FR2972461A1 - PROCESS FOR PRODUCING SEMICONDUCTOR NANOPARTICLES - Google Patents
PROCESS FOR PRODUCING SEMICONDUCTOR NANOPARTICLES Download PDFInfo
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- FR2972461A1 FR2972461A1 FR1151926A FR1151926A FR2972461A1 FR 2972461 A1 FR2972461 A1 FR 2972461A1 FR 1151926 A FR1151926 A FR 1151926A FR 1151926 A FR1151926 A FR 1151926A FR 2972461 A1 FR2972461 A1 FR 2972461A1
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 28
- 239000004065 semiconductor Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 238000005530 etching Methods 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 13
- 239000011858 nanopowder Substances 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 16
- 238000000151 deposition Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021422 solar-grade silicon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/12—Etching of semiconducting materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y99/00—Subject matter not provided for in other groups of this subclass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
La présente invention concerne un procédé de fabrication de nanoparticules semi-conductrices par gravure électrochimique d'un substrat métallurgique (7), remarquable en ce que le procédé comprend le dopage du substrat (7) sur au moins deux faces (71, 72) de celui-ci.The present invention relates to a method for manufacturing semiconductor nanoparticles by electrochemical etching of a metallurgical substrate (7), which is remarkable in that the method comprises doping the substrate (7) on at least two faces (71, 72) of this one.
Description
i PROCEDE DE FABRICATION DE NANOPARTICULES SEMI-CONDUCTRICES DOMAINE DE L'INVENTION La présente invention concerne le domaine de la fabrication de nano-poudres/nanoparticules semi-conductrices. FIELD OF THE INVENTION The present invention relates to the field of the manufacture of nano-powders / nanoparticles semiconductors.
De telles nano-poudres/nano-particules semi-conductrices peuvent avoir différentes 10 applications. Elles sont par exemple utilisées en tant que moyen d'identification pour le marquage d'objet ou pour la production de l'hydrogène. Such nano-powders / nanoparticles may have different applications. For example, they are used as means of identification for the object marking or for the production of hydrogen.
ARRIERE-PLAN DE L'INVENTION BACKGROUND OF THE INVENTION
15 On connaît différents procédés de fabrication de nanostructures semi-conductrices par gravure chimique ou électrochimique de substrat de silicium. Le document [G. Korotcenkov, B.K. Cho, Crit. Rev. Solid State & Mat. Sci., vol. 35, 2010, pp. 153-260] décrit un exemple de procédé pour la fabrication de nanostructures semi-conductrices. 20 Un exemple de procédé de fabrication de nanoparticules de silicium comprend l'introduction d'une plaque de silicium monocristallin plongée dans un bain d'acide fluorhydrique dans lequel sont disposés une anode et une cathode. Les plaques de silicium monocristallin ayant les mêmes propriétés d'une plaque à l'autre, ce type de 25 procédé de fabrication de nanostructures est facilement reproductible. Various methods of manufacturing semiconductor nanostructures by chemical or electrochemical etching of silicon substrate are known. The document [G. Korotcenkov, B.K. Cho, Crit. Rev. Solid State & Mat. Sci., Vol. 35, 2010, pp. 153-260] describes an exemplary method for the manufacture of semiconductor nanostructures. An example of a method for manufacturing silicon nanoparticles comprises introducing a monocrystalline silicon plate immersed in a hydrofluoric acid bath in which an anode and a cathode are disposed. Because monocrystalline silicon plates have the same plate-to-plate properties, this type of nanostructure fabrication process is easily reproducible.
Un but de la présente invention est d'augmenter la rentabilité des procédés de fabrication de nanoparticules semi-conductrices existants.5 BREVE DESCRIPTION DE L'INVENTION An object of the present invention is to increase the profitability of existing semiconductor nanoparticle manufacturing processes. BRIEF DESCRIPTION OF THE INVENTION
A cet effet, l'invention propose un procédé de fabrication de nanoparticules semi-conductrices par gravure électrochimique d'un substrat de qualité métallurgique dopé sur au moins deux faces. For this purpose, the invention proposes a method for manufacturing semiconductor nanoparticles by electrochemical etching of a substrate of metallurgical quality doped on at least two faces.
On entend, dans le cadre de la présente invention, par « dopage » d'une face du substrat, le fait d'homogénéiser et/ou d'améliorer la conductivité du substrat métallurgique sur ladite face. In the context of the present invention, the term "doping" of a face of the substrate is intended to mean homogenizing and / or improving the conductivity of the metallurgical substrate on said face.
Le dopage peut être un dopage par introduction d'impureté dans le substrat ou un dopage optique par émission de lumière, ces différents types de dopage permettant la génération de charges électriques : - dans le cas de l'introduction d'une impureté, on génère une charge libre suite à la différence des valences des atomes et - dans le cas de l'émission de lumière, on génère également une charge libre en utilisant le phénomène d'absorption d'un photon. The doping may be a doping by introduction of impurity into the substrate or optical doping by light emission, these different types of doping allowing the generation of electric charges: in the case of the introduction of an impurity, one generates a free charge following the difference of the valences of the atoms and - in the case of the emission of light, one also generates a free charge by using the phenomenon of absorption of a photon.
Des aspects préférés mais non limitatifs du procédé selon l'invention sont les suivants : - le substrat est du silicium métallurgique, les nanoparticules semi-conductrices étant obtenues par gravure électrochimique du substrat de silicium métallurgique ; - l'étape de dopage comprend la fabrication du contact ohmique face arrière par: - dépôt d'aluminium sur la face arrière du substrat pour obtenir un substrat comprenant une couche d'aluminium, et - recuit du substrat comprenant la couche d'aluminium ; - la durée de l'étape de recuit est comprise entre 1 min et 1 heure ; - l'épaisseur de la couche d'aluminium est comprise entre 10 nm et 10 pm ; - le procédé comprend éventuellement une étape de retrait de la couche d'aluminium après l'étape de recuit ; - l'étape de dopage du substrat comprend l'éclairage face avant du substrat à l'aide d'une source de lumière blanche produisant un rayonnement lumineux. Preferred but non-limiting aspects of the process according to the invention are the following: the substrate is metallurgical silicon, the semiconductor nanoparticles being obtained by electrochemical etching of the metallurgical silicon substrate; the doping step comprises the fabrication of the backside ohmic contact by: deposition of aluminum on the rear face of the substrate to obtain a substrate comprising an aluminum layer, and annealing of the substrate comprising the aluminum layer; the duration of the annealing step is between 1 min and 1 hour; the thickness of the aluminum layer is between 10 nm and 10 μm; the process optionally comprises a step of removing the aluminum layer after the annealing step; the step of doping the substrate comprises illuminating the front face of the substrate with the aid of a source of white light producing a luminous radiation.
L'invention concerne également une nano-poudre de nanoparticules semi-conductrices, caractérisé en ce que les particules semi-conductrices sont obtenues par le procédé de fabrication tel que décrit ci-dessus. BREVE DESCRIPTION DES DESSINS The invention also relates to a nano-powder of semiconductor nanoparticles, characterized in that the semiconductor particles are obtained by the manufacturing method as described above. BRIEF DESCRIPTION OF THE DRAWINGS
D'autres avantages et caractéristiques ressortiront mieux de la description qui va suivre de plusieurs variantes d'exécution, données à titre d'exemples non limitatifs, à 15 partir des dessins annexés sur lesquels les figures 1 à 3 qui illustrent différents exemples de procédés de fabrication de nanoparticules semi-conductrices à partir d'un substrat de silicium métallurgique. Other advantages and features will become more apparent from the following description of several variant embodiments, given by way of non-limiting examples, from the attached drawings in which FIGS. 1 to 3 which illustrate various examples of manufacturing semiconductor nanoparticles from a metallurgical silicon substrate.
DESCRIPTION DETAILLEE DE L'INVENTION L'invention propose donc un procédé de fabrication de nano-poudres/nano-particules semi-conductrices à partir d'un substrat de qualité métallurgique. DETAILED DESCRIPTION OF THE INVENTION The invention therefore proposes a process for manufacturing semiconductor nano-powders / nanoparticles from a metallurgical grade substrate.
On va maintenant décrire plus en détail l'invention en référence à un substrat de 25 silicium métallurgique, étant entendu que d'autres types de substrats peuvent être utilisés. The invention will now be described in more detail with reference to a metallurgical silicon substrate, it being understood that other types of substrates may be used.
Le silicium n'existe pas naturellement à l'état libre sur la Terre, mais il est très abondant sous forme d'oxydes, par exemple la silice ou les silicates. Le silicium est 30 extrait de son oxyde par des procédés métallurgiques, et son niveau de pureté 10 20 dépend de son utilisation finale. On distingue trois niveaux de pureté du silicium, désignés en fonction de l'utilisation : - le silicium métallurgique (pureté 99 %), - le silicium de qualité solaire (pureté 99,999 9 %), - le silicium de qualité électronique (pureté 99,999 999 99 %). Silicon does not exist naturally in the free state on the Earth, but it is very abundant in the form of oxides, for example silica or silicates. Silicon is extracted from its oxide by metallurgical processes, and its level of purity depends on its end use. There are three levels of silicon purity, designated according to use: - metallurgical silicon (purity 99%), - solar grade silicon (purity 99.999 9%), - electronic grade silicon (purity 99.999 999 99%).
Les procédés existants de fabrication de nanostructures de silicium par gravure électrochimique utilisent généralement des substrats de silicium de qualité solaire voire électronique pour l'obtention de nano-poudres/nano-particules semi- conductrices. En effet, ce type de substrat présente une résistivité électrique homogène sur tout son volume. L'homme du métier sait qu'il est nécessaire de disposer d'un substrat de grande pureté pour que la gravure électrochimique soit homogène et permette l'obtention de nano-poudres/nano-particules semi-conductrices. The existing processes for the fabrication of silicon nanostructures by electrochemical etching generally use silicon substrates of solar or even electronic quality to obtain nanopowder nanoparticles / nanoparticles. Indeed, this type of substrate has a homogeneous electrical resistivity throughout its volume. Those skilled in the art know that it is necessary to have a substrate of high purity so that the electrochemical etching is homogeneous and allows the production of nano-powders / nanoparticles semiconductors.
La gravure électrochimique de silicium métallurgique ne permet pas l'obtention facile de nano-poudres/nano-particules semi-conductrices du fait de l'inhomogénéité (en termes de composition chimique et cristallinité) des substrats de silicium métallurgique. Certaines régions de résistivité faible 1 sont gravées électro- chimiquement, tandis que d'autres régions de résistivité plus forte 2 ne sont pas gravées. Par ailleurs, la gravure se produit généralement le long des joints de grain 3 du substrat de silicium métallurgique, c'est à dire à la jonction entre deux régions du substrat d'orientations cristallines différentes. Ceci induit la production d'amas 4 de silicium et non de nanoparticules semi-conductrices, ce qui est inacceptable. The electrochemical etching of metallurgical silicon does not make it easy to obtain nano-powders / nanoparticles because of the inhomogeneity (in terms of chemical composition and crystallinity) of the metallurgical silicon substrates. Some regions of low resistivity 1 are etched electrochemically, while other regions of higher resistivity 2 are not etched. Furthermore, the etching generally occurs along the grain boundaries 3 of the metallurgical silicon substrate, that is to say at the junction between two regions of the substrate of different crystalline orientations. This induces the production of clusters 4 of silicon and not of semiconductor nanoparticles, which is unacceptable.
C'est pourquoi les procédés de fabrication de nanoparticules semi-conductrices utilisent généralement des substrats de silicium de grande pureté et homogène. This is why the processes for manufacturing semiconductor nanoparticles generally use silicon substrates of high purity and homogeneity.
Toutefois, les substrats de grande pureté ont un coût non négligeable, ce qui diminue la rentabilité des procédés de fabrication de nanoparticules semi-conductrices. However, substrates of high purity have a significant cost, which decreases the profitability of semiconductor nanoparticle manufacturing processes.
L'invention propose un procédé de fabrication de nanoparticules semi-conductrices plus rentable que les procédés de fabrication existants. The invention provides a method of manufacturing semiconductor nanoparticles more cost effective than existing manufacturing processes.
En référence à la figure 2, on a illustré une première variante du procédé de fabrication de nanoparticules semi-conductrices. Dans cette variante de réalisation, les nanoparticules sont obtenues par gravure d'un substrat de silicium métallurgique 7, de préférence massif. With reference to FIG. 2, a first variant of the method for manufacturing semiconductor nanoparticles has been illustrated. In this variant embodiment, the nanoparticles are obtained by etching a metallurgical silicon substrate 7, which is preferably solid.
On entend, dans le cadre de la présente invention, par « silicium métallurgique », un substrat de silicium ayant un taux d'impureté supérieur à 0,001 %. In the context of the present invention, the term "metallurgical silicon" means a silicon substrate having an impurity level greater than 0.001%.
On entend, dans le cadre de la présente invention, par « substrat massif », tout composé chimique constitué principalement des atomes de silicium (Si) liés chimiquement (de manière covalente) entre eux et dont au moins une dimension linéaire de la taille (hauteur, largeur, longueur, diamètre, etc.) est supérieure à 1 mm. In the context of the present invention, the term "solid substrate" is intended to mean any chemical compound consisting mainly of silicon (Si) atoms chemically bonded (covalently) to one another and at least one of which is linear in size (height). width, length, diameter, etc.) is greater than 1 mm.
De préférence, la gravure du substrat de silicium métallurgique 7 est obtenue par une attaque électrochimique du substrat de silicium métallurgique 7. Par exemple, la gravure est obtenue par une attaque électrochimique durant laquelle le substrat de silicium métallurgique 7 se trouve en contact avec un électrolyte 5 comprenant au moins un acide (acide fluorhydrique, par exemple). Preferably, the etching of the metallurgical silicon substrate 7 is obtained by an electrochemical etching of the metallurgical silicon substrate 7. For example, the etching is obtained by an electrochemical etching during which the metallurgical silicon substrate 7 is in contact with an electrolyte Comprising at least one acid (hydrofluoric acid, for example).
Ce substrat est traversé par un courant électrique. Les paramètres de gravure tels que la densité de courant, la composition chimique, la concentration de l'électrolyte, la pression et la température ambiante seront choisis en fonction des besoins (vitesse de gravure, porosité, etc.). This substrate is traversed by an electric current. The etching parameters such as the current density, the chemical composition, the concentration of the electrolyte, the pressure and the ambient temperature will be chosen according to the needs (etch rate, porosity, etc.).
On obtient ainsi des nano-poudres/nanoparticules semi-conductrices, les paramètres de la gravure étant préférentiellement choisis pour permettre l'obtention de nanoparticules de taille inférieure ou égale à 50 nanomètres, préférentiellement inférieure ou égale à 7 nanomètres, et encore plus préférentiellement inférieure ou égale à 5 nanomètres. Semiconductor nano-powders / nanoparticles are thus obtained, the etching parameters being preferably chosen to enable nanoparticles of size less than or equal to 50 nanometers to be obtained, preferably less than or equal to 7 nanometers, and even more preferentially lower. or equal to 5 nanometers.
Pour permettre la gravure électrochimique du substrat de silicium métallurgique 7, le procédé selon l'invention comprend le dopage du substrat sur au moins deux faces de celui-ci. Plus précisément, le procédé de fabrication comprend le dopage du substrat sur deux faces opposées, par exemple les faces avant 71 et arrière 72 de celui-ci. To enable the electrochemical etching of the metallurgical silicon substrate 7, the method according to the invention comprises the doping of the substrate on at least two faces thereof. More specifically, the manufacturing method comprises the doping of the substrate on two opposite faces, for example the front 71 and rear 72 faces thereof.
Ceci permet d'homogénéiser la conductivité du substrat métallurgique sur les faces avant et arrière 71, 72, de sorte que la gravure électrochimique d'un substrat massif de silicium métallurgique 7 pour obtenir des nanoparticules semi-conductrices devient possible. This makes it possible to homogenize the conductivity of the metallurgical substrate on the front and rear faces 71, 72, so that the electrochemical etching of a solid metallurgical silicon substrate 7 to obtain semiconductor nanoparticles becomes possible.
Dans un mode de réalisation, le dopage face arrière est réalisé par dépôt d'une couche d'aluminium 6 sur la face arrière 72 du substrat 7, et recuit du substrat 7 comprenant la couche d'aluminium 6. L'étape de recuit permet la diffusion de l'aluminium dans l'épaisseur du substrat de silicium métallurgique 7 pour en améliorer la conductivité. In one embodiment, the backside doping is performed by deposition of an aluminum layer 6 on the rear face 72 of the substrate 7, and annealing of the substrate 7 comprising the aluminum layer 6. The annealing step allows diffusion of the aluminum in the thickness of the metallurgical silicon substrate 7 to improve the conductivity thereof.
Le dépôt peut être réalisé par différentes techniques connues de l'homme du métier. Par exemple, l'aluminium peut également être déposé sur le substrat 7 par pulvérisation, ou encore par une technique de dépôt par voie électrolytique. Deposition can be achieved by various techniques known to those skilled in the art. For example, the aluminum can also be deposited on the substrate 7 by spraying, or else by an electrolytic deposition technique.
La durée de l'étape de recuit peut varier en fonction par exemple de l'épaisseur de la couche d'aluminium. De préférence, la durée de l'étape de recuit est comprise entre 1 min et 1 heure. The duration of the annealing step may vary depending, for example, on the thickness of the aluminum layer. Preferably, the duration of the annealing step is between 1 min and 1 hour.
Le dopage face avant 71 peut être réalisé par différentes techniques. Dans un mode de réalisation, on propose d'effectuer un éclairage de celle-ci à l'aide d'une source de lumière blanche produisant un rayonnement lumineux. Dans ce cas, l'éclairage de la face avant 71 du substrat 7 est réalisé tout au long de la gravure électrochimique de celui-ci. Front-end doping 71 can be achieved by various techniques. In one embodiment, it is proposed to illuminate the same with a white light source producing light radiation. In this case, the illumination of the front face 71 of the substrate 7 is made throughout the electrochemical etching thereof.
L'éclairage de la face avant 71 du substrat 7 permet d'homogénéiser la résistivité photo-induite et d'assurer sa bonne conductivité électrique. The illumination of the front face 71 of the substrate 7 makes it possible to homogenise the photoinduced resistivity and to ensure its good electrical conductivity.
On va maintenant décrire plus en détail le principe de fonctionnement du procédé de fabrication de nanoparticules semi-conductrices selon l'invention. Dans une première étape, on dépose une couche métallique 6 telle que de l'aluminium sur la face arrière 72 du substrat de silicium métallurgique 7. We will now describe in more detail the operating principle of the method for manufacturing semiconductor nanoparticles according to the invention. In a first step, a metal layer 6 such as aluminum is deposited on the rear face 72 of the metallurgical silicon substrate 7.
On effectue ensuite un recuit du substrat 7 comprenant la couche d'aluminium 6. 15 Durant le recuit, l'aluminium se diffuse à l'intérieur du substrat 7. Ceci permet d'homogénéiser la conductivité du substrat 7 sur la face arrière 72. Annealing of the substrate 7 comprising the aluminum layer 6 is then carried out. During the annealing, the aluminum diffuses inside the substrate 7. This makes it possible to homogenize the conductivity of the substrate 7 on the rear face 72.
Il est optionnellement possible de retirer la couche d'aluminium après l'étape de recuit. Cette étape dépend du nombre de substrats que l'on souhaite graver électro-20 chimiquement dans un même bain. It is optionally possible to remove the aluminum layer after the annealing step. This step depends on the number of substrates that it is desired to etch electro-chemically in the same bath.
Par exemple, si l'on ne souhaite graver qu'un seul substrat, il n'est pas nécessaire de retirer la couche d'aluminium 6: il est possible de disposer le substrat 7 horizontalement dans un bain d'acide fluorhydrique 5, la face d'aluminium n'étant pas 25 en contact avec la solution d'acide fluorhydrique, comme illustré à la figure 2. For example, if it is desired to engrave only one substrate, it is not necessary to remove the aluminum layer 6: it is possible to arrange the substrate 7 horizontally in a hydrofluoric acid bath 5, the aluminum face not in contact with the hydrofluoric acid solution, as shown in FIG.
Si par contre, on souhaite graver plusieurs substrats en parallèle dans le bain d'acide fluorhydrique, on retirera préférentiellement la couche d'aluminium de chaque substrat 7 et on les disposera verticalement dans la solution d'acide fluorhydrique 5, 3o comme illustré à la figure 3. 10 2972461 s On dispose le (ou les) substrat(s) de silicium métallurgique dopé(s) face arrière 72 dans la solution d'acide fluorhydrique 5. If, on the other hand, it is desired to etch several substrates in parallel in the hydrofluoric acid bath, the aluminum layer will preferably be removed from each substrate 7 and placed vertically in the hydrofluoric acid solution 5, as shown in FIG. FIG. 3. 2972461 s The rear-doped doped metallurgical silicon substrate (s) 72 is placed in the hydrofluoric acid solution 5.
On éclaire ensuite la face avant 71 du ou des substrats 7 en utilisant une source de 5 lumière blanche tel qu'une lampe émettant un rayonnement lumineux blanc. The front face 71 of the substrate (s) 7 is then illuminated using a white light source such as a lamp emitting white light radiation.
Enfin, on applique un courant électrique dans la solution d'acide fluorhydrique 5. La gravure électrochimique du substrat 7 dopé sur ses deux faces 71, 72 débute alors et permet l'obtention de nanoparticules semi-conductrices. Avec le procédé selon l'invention, les nanoparticules semi-conductrices sont faciles à produire en grande quantité et à bas coût. Finally, an electric current is applied in the hydrofluoric acid solution 5. The electrochemical etching of the substrate 7 doped on its two faces 71, 72 then begins and allows the production of semiconductor nanoparticles. With the method according to the invention, the semiconductor nanoparticles are easy to produce in large quantities and at low cost.
Il est bien évident que les exemples qui viennent d'être donnés ne sont que des 15 illustrations particulières en aucun cas limitatives. It is obvious that the examples which have just been given are only particular illustrations that are in no way limiting.
Claims (9)
Priority Applications (7)
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EP12707779.0A EP2683856B1 (en) | 2011-03-09 | 2012-03-09 | Process for manufacturing silicon-based nanoparticles from metallurgical-grade silicon or refined metallurgical-grade silicon |
US14/004,018 US9352969B2 (en) | 2011-03-09 | 2012-03-09 | Process for manufacturing silicon-based nanoparticles from metallurgical-grade silicon or refined metallurgical-grade silicon |
CA2829147A CA2829147C (en) | 2011-03-09 | 2012-03-09 | Process for manufacturing silicon-based nanoparticles from metallurgical-grade silicon or refined metallurgical-grade silicon |
JP2013557113A JP6117118B2 (en) | 2011-03-09 | 2012-03-09 | Method for generating hydrogen from silicon-based nanopowder |
PCT/EP2012/054124 WO2012120117A1 (en) | 2011-03-09 | 2012-03-09 | Process for manufacturing silicon-based nanoparticles from metallurgical-grade silicon or refined metallurgical-grade silicon |
CN201280022365.3A CN103635612B (en) | 2011-03-09 | 2012-03-09 | By metallurgical grade silicon or the method for affinage metallurgy level silicon nano particle of the manufacture based on silicon |
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US20230365415A1 (en) * | 2020-04-02 | 2023-11-16 | Bosquet Silicon Corp. | Composite material |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997006550A1 (en) * | 1995-08-03 | 1997-02-20 | Massachusetts Institute Of Technology | Method for producing semiconductor particles |
US6328876B1 (en) * | 1997-07-28 | 2001-12-11 | Nft Nanofiltertechnik Gesellschaft Mit Beschankter Haftung | Method for producting a filter |
US20040126072A1 (en) * | 2001-08-02 | 2004-07-01 | Hoon Lee Howard Wing | Optical devices with engineered nonlinear nanocomposite materials |
US20080280140A1 (en) * | 2007-04-27 | 2008-11-13 | Mauro Ferrari | Porous particles and methods of making thereof |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4124410A (en) * | 1977-11-21 | 1978-11-07 | Union Carbide Corporation | Silicon solar cells with low-cost substrates |
JPH0459601A (en) * | 1990-06-26 | 1992-02-26 | Asahi Chem Ind Co Ltd | Production of hydrogen |
US5208001A (en) * | 1991-06-20 | 1993-05-04 | Texas Instruments Incorporated | Method for silicon purification |
US5445718A (en) * | 1994-01-24 | 1995-08-29 | General Motors Corporation | Electrochemical etch-stop on n-type silicon by injecting holes from a shallow p-type layer |
US6585947B1 (en) * | 1999-10-22 | 2003-07-01 | The Board Of Trustess Of The University Of Illinois | Method for producing silicon nanoparticles |
US6743406B2 (en) * | 1999-10-22 | 2004-06-01 | The Board Of Trustees Of The University Of Illinois | Family of discretely sized silicon nanoparticles and method for producing the same |
US6992298B2 (en) * | 2001-11-21 | 2006-01-31 | The Board Of Trustees Of The University Of Illinois | Coated spherical silicon nanoparticle thin film UV detector with UV response and method of making |
JP2004115349A (en) * | 2002-09-30 | 2004-04-15 | Honda Motor Co Ltd | Hydrogen generation process |
JP2004307328A (en) * | 2003-03-25 | 2004-11-04 | Sanyo Electric Co Ltd | Hydrogen producing method, hydrogen producing apparatus and motor equipped with the same |
FR2858313B1 (en) * | 2003-07-28 | 2005-12-16 | Centre Nat Rech Scient | HYDROGEN RESERVOIR BASED ON SILICON NANO STRUCTURES |
JP2007513048A (en) * | 2003-12-04 | 2007-05-24 | ダウ・コーニング・コーポレイション | Method for removing impurities from metallurgical grade silicon to produce solar grade silicon |
JP2005285380A (en) | 2004-03-26 | 2005-10-13 | Quantum 14:Kk | Diode element and device using the same |
EP1899261A2 (en) * | 2005-06-30 | 2008-03-19 | University of Cape Town | Semiconducting nanoparticles with surface modification |
GB0515353D0 (en) | 2005-07-27 | 2005-08-31 | Psimedica Ltd | Food |
JP4837465B2 (en) | 2006-07-11 | 2011-12-14 | 日揮触媒化成株式会社 | Method for producing silicon fine particle-containing liquid and method for producing silicon fine particle |
AU2008275181B2 (en) | 2007-07-10 | 2014-06-26 | The Regents Of The University Of California | Materials and methods for delivering compositions to selected tissues |
GB0713898D0 (en) * | 2007-07-17 | 2007-08-29 | Nexeon Ltd | A method of fabricating structured particles composed of silcon or a silicon-based material and their use in lithium rechargeable batteries |
-
2011
- 2011-03-09 FR FR1151926A patent/FR2972461B1/en active Active
-
2012
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997006550A1 (en) * | 1995-08-03 | 1997-02-20 | Massachusetts Institute Of Technology | Method for producing semiconductor particles |
US6328876B1 (en) * | 1997-07-28 | 2001-12-11 | Nft Nanofiltertechnik Gesellschaft Mit Beschankter Haftung | Method for producting a filter |
US20040126072A1 (en) * | 2001-08-02 | 2004-07-01 | Hoon Lee Howard Wing | Optical devices with engineered nonlinear nanocomposite materials |
US20080280140A1 (en) * | 2007-04-27 | 2008-11-13 | Mauro Ferrari | Porous particles and methods of making thereof |
Non-Patent Citations (1)
Title |
---|
NOBUYOSHI KOSHIDA ET AL: "EFFICIENT VISIBLE PHOTOLUMINESCENCE FROM POROUS SILICON", JAPANESE JOURNAL OF APPLIED PHYSICS, JAPAN SOCIETY OF APPLIED PHYSICS, JP, vol. 30, no. 7B PART 02, 15 July 1991 (1991-07-15), pages L1221 - L1223, XP000237709, ISSN: 0021-4922, DOI: 10.1143/JJAP.30.L1221 * |
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CN103635612A (en) | 2014-03-12 |
US9352969B2 (en) | 2016-05-31 |
CN103635612B (en) | 2017-07-11 |
EP2683856B1 (en) | 2017-08-09 |
EP2683856A1 (en) | 2014-01-15 |
JP6117118B2 (en) | 2017-04-19 |
FR2972461B1 (en) | 2021-01-01 |
CA2829147A1 (en) | 2012-09-13 |
CA2829147C (en) | 2019-04-30 |
US20130341234A1 (en) | 2013-12-26 |
JP2014518535A (en) | 2014-07-31 |
WO2012120117A1 (en) | 2012-09-13 |
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